Abstract: Sodium filled skutterudite NaFe₄P₁₂ whiskers and nanowires were prepared by a hydrothermal synthesis method. Skutterudite-polyaniline thermoelectric composite was prepared by in situ compounding using an emulsion polymerization method. The nanowires and whiskers as well as the composites were characterized by infrared spectra UV/VIs spectra and X-ray diffraction. Transmission electron microscope observation on the composite was carried out to investigate the morphology and growth mechanism of polyaniline on the surface of the skutterudite wires. Polyaniline can be compounded on the surface of the wires. In some samples, polyaniline grows as a brush structure on the surface of the NaFe₄P₁₂ whisker.